CN105390746A - Electrolyte for lithium battery and lithium battery including the same - Google Patents
Electrolyte for lithium battery and lithium battery including the same Download PDFInfo
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- CN105390746A CN105390746A CN201510526210.9A CN201510526210A CN105390746A CN 105390746 A CN105390746 A CN 105390746A CN 201510526210 A CN201510526210 A CN 201510526210A CN 105390746 A CN105390746 A CN 105390746A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Abstract
An electrolyte for a lithium battery and a lithium battery including the electrolyte. The electrolyte is employed in the lithium battery so as to improve cycle characteristics of the lithium battery that is operable at high voltages.
Description
The cross reference of related application
This application claims priority and the rights and interests of the korean patent application No.10-2014-0111045 that on August 25th, 2014 submits in Korean Intellectual Property Office, by its disclosure by reference in being all incorporated herein.
Technical field
One or more Example embodiments relate to for lithium battery electrolyte and comprise described electrolytical lithium battery.
Background technology
For using the lithium secondary battery of (utilization) to have for the large discharge voltage of at least twice of the discharge voltage of conventional batteries in information and the portable electron device communicated (comprising PDA, mobile phone and kneetop computer) or in electric bicycle or electric motor car.Therefore, lithium secondary battery can have high energy density.
Lithium secondary battery comprise each self-contained can carry out the embedding of lithium ion and the active material of deintercalation positive pole and negative pole and the organic electrolyte solution of filling between a positive electrode and a negative electrode or polymer dielectric.Here, in positive pole and negative pole, during the embedding/deintercalation of lithium ion, oxidation and reduction reaction occur, and produce electric energy thus.
The use (utilization) expanded in electric motor car and energy storage field along with lithium secondary battery, has become can obtain for using the electrode active material of (utilization) under high voltages.The negative electrode active material of relative low potential has caused electrolytical narrower electromotive force window with the use (utilization) of the positive active material of relative high potential, electrolyte is become and more may decompose on the surface of positive pole/negative pole.In addition, the lithium secondary battery for electric motor car and energy storage may be exposed to outside high ambient conditions, and during instantaneous charging and discharging, the temperature of these lithium secondary batteries can raise.Therefore, in such high ambient conditions, the useful life (life-span) of lithium secondary battery and the amount of stored energy can reduce.
Therefore, for the application of lithium battery in electric automobiles etc., lithium battery stability under high voltages and cycle characteristics are the things of important concern.
Summary of the invention
Relate to the electrolyte for lithium battery according to the aspect of one or more Example embodiments, described electrolyte helps improve lithium battery cycle characteristics under high voltages.
Relate to according to the aspect of one or more Example embodiments and comprise described electrolytical lithium battery.
Extra aspect will partly be set forth in the description that follows, and partly will be distinct from described description, or learns by the practice of provided execution mode.
According to one or more Example embodiments, the electrolyte for lithium battery comprises: non-aqueous organic solvent; The first compound represented by formula 1; With the second compound represented by formula 2:
Formula 1
In formula 1,
A is boron (B) or phosphorus (P);
X is halogen atom;
When A is boron (B), n equals 1 and m equals 1; With
When A is phosphorus (P), n equals 1 and m equals 2, or n equals 2 and m equals 1.
Formula 2
In formula 2,
R
1-R
9hydrogen, deuterium, halogen atom, hydroxyl (-OH), cyano group, nitro, amino, amidino groups, diazanyl, hydrazone group, hydroxy-acid group or its salt, sulfonic acid group or its salt, phosphate group or its salt, thiol group (-SH) ,-C (=O)-H, substituted or unsubstituted C can be selected from independently of one another
1-C
60alkyl, substituted or unsubstituted C
2-C
60thiazolinyl, substituted or unsubstituted C
2-C
60alkynyl, substituted or unsubstituted C
3-C
10cycloalkyl, substituted or unsubstituted C
3-C
10heterocyclylalkyl, substituted or unsubstituted C
3-C
10cycloalkenyl group, substituted or unsubstituted C
2-C
10heterocycloalkenyl, substituted or unsubstituted C
6-C
60aryl and substituted or unsubstituted C
2-C
60heteroaryl; With
N is 0 or 1.
According to one or more Example embodiments, lithium battery comprises described electrolyte.
Accompanying drawing explanation
From the following description of the Example embodiments considered by reference to the accompanying drawings, these and/or other side will become distinct and be easier to understand, wherein:
Fig. 1 illustrates the schematic cross section according to the structure of the lithium battery of Example embodiments;
Fig. 2 is the figure of confining force to cycle-index, the capability retention of the lithium battery that its display is prepared according to embodiment 1a-1d and comparative example 1a-1c;
Fig. 3 is the figure of confining force to cycle-index, the capability retention of the lithium battery that its display is prepared according to embodiment 2 and comparative example 2a-2b;
Fig. 4 A and 4B is that intensity is to the figure combining energy, its illustrate after initial charge and discharge cycles from x-ray photoelectron spectroscopy (XPS) data of the surfacing of the positive pole of the lithium battery prepared according to embodiment 2 and comparative example 2a-2b, wherein Fig. 4 A be presented at O1s peak place measure data and Fig. 4 B be presented at F1s peak place measure data; With
Fig. 5 is the figure of confining force to cycle-index, the capability retention of the lithium battery that its display is prepared according to embodiment 3a-3c and comparative example 3a-3b.
Embodiment
Be introduced to the Example embodiments of the electrolyte and the described electrolytical lithium battery of employing that are used for lithium battery in more detail now, the example is illustrated in accompanying drawing, and wherein identical Reference numeral refers to identical key element all the time.In this, this Example embodiments can have different forms and should not be construed as limited to the description of setting forth herein.Therefore, below by means of only described Example embodiments is described with reference to the drawings, so that the aspect of this description to be described.As used in this article, term "and/or" comprises one or more any and whole combination of associated listed items.Statement such as " at least one (individual) " when before or after key element list, is modified whole key element list and is not modified the independent key element of described list.In addition, when describing embodiments of the present invention, the use of "available" refers to " one or more execution mode of the present invention ".As used in this article, term " substantially ", " about " and similar term use as approximate term and do not use as the term of degree, and meant for illustration one of skill in the art will recognize that measure or calculating value in in deviation.In addition, any number range intention enumerated herein is included in cited scope all subranges of the identical numerical precision comprised.Such as, the scope intention of " 1.0-10.0 " is included in (and comprising cited minimum value 1.0 and cited maximum 10.0) between cited minimum value 1.0 and cited maximum 10.0, namely there are the minimum value being equal to or greater than 1.0 and all subranges of maximum being equal to or less than 10.0, such as, 2.4-7.6.Any greatest measure enumerated herein limits intention and comprises all lower numerical definiteness wherein comprised, and any minimum value restriction intention enumerated in this specification comprises all higher numerical definiteness wherein comprised.Therefore, applicant retains following right: revise this specification (comprising claim), to enumerate any subrange in the scope that is included in and enumerates clearly clearly herein.All such scope intentions are described in this manual inherently.
According to an execution mode, the electrolyte for lithium battery comprises: non-aqueous organic solvent; The first compound represented by following formula 1; With the second compound represented by following formula 2:
Formula 1
In above formula 1,
A can be boron (B) or phosphorus (P),
X can be halogen atom,
When A is boron (B), n can equal 1 and m can equal 1, and
When A is phosphorus (P), n can equal 1 and m can equal 2, or n can equal 2 and m can equal 1.
Formula 2
In above formula 2,
R
1-R
9hydrogen, deuterium, halogen, hydroxyl (-OH), cyano group, nitro, amino, amidino groups, diazanyl, hydrazone group, hydroxy-acid group or its salt, sulfonic acid group or its salt, phosphate group or its salt, thiol group (-SH) ,-C (=O)-H, substituted or unsubstituted C can be selected from independently of one another
1-C
60alkyl, substituted or unsubstituted C
2-C
60thiazolinyl, substituted or unsubstituted C
2-C
60alkynyl, substituted or unsubstituted C
3-C
10cycloalkyl, substituted or unsubstituted C
3-C
10heterocyclylalkyl, substituted or unsubstituted C
3-C
10cycloalkenyl group, substituted or unsubstituted C
2-C
10heterocycloalkenyl, substituted or unsubstituted C
6-C
60aryl and substituted or unsubstituted C
2-C
60heteroaryl, and
N is 0 or 1.
Lithium battery such as lithium secondary battery can worsen in charging and discharging cycle period and cause the decomposition of electrolyte on the surface of positive pole and/or negative pole.The electrochemical dissolution occurred on the surface of positive pole between charge period can comprise the reaction of two types: a kind of is the decomposition of non-aqueous organic solvent, and another kind is the decomposition of the lithium salts as solute.The change that these decomposition reactions can not only cause electrolyte to form, and cause the reduction of charging and discharging efficiency.And the catabolite here obtained can form inert coating on the surface of positive pole and/or negative pole, and suppresses the charging and discharging of battery to react.In this, its cycle characteristics can deterioration.
When using the combination of (utilization) described first compound and described second compound as additive agent electrolyte, described first compound forms the firm diaphragm based on LiX with oxalates structure by oxidation.In this, under the high voltage of at least 4.4V, described first compound can realize the stable performance of battery, its good to be enough to reduce or prevent solvent oxidized/decompose and metal ion by wash-out.In addition, described second compound can form firm coordination (such as, corrdination type) film to present the effect forming firmer film simultaneously on active material.Thus, the formation of cathode film can suppress the deterioration of the battery when electrochemical dissolution.In addition, described second compound also can suppress the decomposition of lithium salts, and therefore, can reduce side effect simultaneously and suppress gas to produce, help improve the stability of battery thus.
Substituent definition used herein will be described below.
Term used herein " alkyl " group refers to the group deriving from completely saturated, branching or nonbranched (or straight chain or line style) hydrocarbon.
The limiting examples of described " alkyl " group comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, neopentyl, isopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethyl amyl group, 2,3-dimethyl amyl group and n-heptyls.
At least one hydrogen atom of described " alkyl " group can be substituted as follows: halogen atom, the C replaced by halogen atom
1-C
20alkyl (such as, CF
3, CHF
2, CH
2f and CCl
3), C
1-C
20alkoxyl, C
2-C
20alkoxyalkyl, hydroxyl, nitro, cyano group, amino, amidino groups, diazanyl, hydrazone group, carboxyl or its salt, sulfonyl, sulfamoyl, sulfonic acid group or its salt, phosphate group or its salt, C
1-C
20alkyl, C
2-C
20thiazolinyl, C
2-C
20alkynyl, C
1-C
20assorted alkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
6-C
20heteroaryl, C
6-C
20heteroaryloxy, C
6-C
20heteroaryloxyalkyl and/or C
6-C
20heteroarylalkyl.
Term used herein " halogen atom " refers to fluorine, bromine, chlorine and/or iodine.
Term used herein is " by the C that halogen atom replaces
1-C
20alkyl " refer to the C replaced by least one halogen group
1-C
20alkyl; And its limiting examples comprises single haloalkyl, dihalo alkyl and multi-haloalkyl, comprises whole haloalkyl.
Described single haloalkyl can refer to the alkyl comprising iodine, bromine, chlorine or a fluorine atom.Described dihalo alkyl and described multi-haloalkyl can refer to the alkyl with the halogen atom that two or more are same to each other or different to each other.
Term used herein " alkoxyl " group can be represented by alkyl-O-, and wherein term " alkyl " has and identical implication described above.The limiting examples of described alkoxyl comprises methoxyl group, ethyoxyl, propoxyl group, 2-propoxyl group, butoxy, tert-butoxy, amoxy and own oxygen base.At least one hydrogen atom of described alkoxyl can be substituted by with the substituting group used in alkyl described above.
Term used herein " alkoxyalkyl " group refers to the alkyl that alkoxy replaces.At least one hydrogen atom of described alkoxyalkyl can be substituted by with the identical substituting group used in described alkyl.Similarly, term used herein " alkoxyalkyl of replacement " refers to the alkoxyalkyl moieties of replacement.
Term used herein " thiazolinyl " group refers to the group of branching or the nonbranched hydrocarbon deriving from and have at least one carbon-to-carbon double bond.The limiting examples of described thiazolinyl comprises vinyl, pi-allyl, cyclobutenyl, isopropenyl and isobutenyl.At least one hydrogen atom of described thiazolinyl can be substituted by with the identical substituting group used in alkyl described above.
Term used herein " alkynyl " group refers to the group of branching or the nonbranched hydrocarbon deriving from and have at least one carbon-to-carbon triple bond.The limiting examples of described alkynyl comprises acetenyl, butynyl, butynyl and isopropynyl.
At least one hydrogen atom of described " alkynyl " can be substituted by with the identical substituting group used in alkyl described above.
Term " aryl " group used in this article be used alone or in combination refers to the aromatic hydrocarbon radical comprising at least one ring.
Term used herein " aryl " group is interpreted as comprising the group with the aromatic ring being fused at least one cycloalkyl ring.
The limiting examples of described " aryl " group is phenyl, naphthyl and tetralyl.
At least one hydrogen atom of described " aryl " group can be substituted by with the identical substituting group used in alkyl described above.
Term used herein " aralkyl " group refers to the alkyl replaced by aryl.The example of described aralkyl comprises benzyl and phenyl-CH
2cH
2-.
Term used herein " aryloxy group " group can be represented by-O-aryl, and the example is phenoxy group.At least one hydrogen atom of described " aryloxy group " group can be substituted by with the identical substituting group used in alkyl described above.
Term " heteroaryl " refers at least one heteroatomic monocycle or bicyclic aromatic group of comprising and being selected from nitrogen (N), oxygen (O), phosphorus (P) and sulphur (S), and wherein the remainder of annular atoms is all carbon atom.Described heteroaryl can comprise such as one to five hetero-atoms, and in some embodiments, can comprise five to ten-ring.In described heteroaryl, P, S or N can exist by multiple oxidised form.
At least one hydrogen atom of described heteroaryl can be substituted by with the identical substituting group used in alkyl described above.
Term used herein " heteroarylalkyl " group refers to the alkyl replaced by heteroaryl.
Term used herein " heteroaryloxy " group refers to-O-heteroaryl moieties.At least one hydrogen atom of described heteroaryloxy can be substituted by with the identical substituting group used in alkyl described above.
Term used herein " Heteroaryloxyalkyl " group refers to the alkyl replaced by heteroaryloxy.At least one hydrogen atom of described heteroaryloxy can be substituted by with the identical substituting group used in alkyl described above.
Term " carbocyclic ring " refers to saturated or that part is undersaturated, non-aromatic monocycle, dicyclo or tricyctic hydrocarbon group.
The example of described monocyclic hydrocarbon group is cyclopenta, cyclopentenyl, cyclohexyl and cyclohexenyl group.The example of described bicyclic hydrocarbon radical is bornyl, decahydro naphthyl, dicyclo [2.1.1] hexyl, dicyclo [2.2.1] heptyl, dicyclo [2.2.1] heptenyl and dicyclo [2.2.2] octyl group.
The example of described tricyctic hydrocarbon group is adamantyl.
At least one hydrogen atom of described " carbocyclic ring " can be substituted by with the identical substituting group used in alkyl described above.
Term used herein " heterocyclic group " refers to the cyclic group be made up of 5-10 annular atoms comprising hetero-atom such as N, S, P or O.The example of described heterocyclic group is pyridine radicals.At least one hydrogen atom of described heterocyclic group can be substituted by with the identical substituting group used in alkyl described above.
Term used herein " heterocyclic oxy group " refers to-O-heterocycle, and at least one hydrogen atom of described heterocyclic oxy group can be substituted by with the identical substituting group used in alkyl described above.
Term used herein " sulfonyl " refers to R "-SO
2-, wherein R " can be hydrogen, alkyl, aryl, heteroaryl, aralkyl, heteroaryl, heteroarylalkyl, alkoxyl, aryloxy group, cycloalkyl or heterocyclic group.
Term used herein " sulfonamides " base refers to H
2nS (O
2)-, alkyl-NHS (O
2)-, (alkyl)
2nS (O
2)-, aryl-NHS (O
2)-, alkyl-(aryl)-NS (O
2)-, (aryl)
2nS (O)
2, heteroaryl-NHS (O
2)-, (aralkyl)-NHS (O
2)-and/or (heteroarylalkyl)-NHS (O
2)-.
At least one hydrogen atom of described sulfamoyl can be substituted by with the identical substituting group used in alkyl described above.
Term used herein " amino " refers to wherein nitrogen-atoms and is covalently bound at least one carbon or heteroatomic situation.The example of described amino is-NH
2with the part replaced.In addition, described amino can comprise wherein nitrogen atom bonding " arylamino " to " alkyl amino " of at least one extra alkyl, wherein nitrogen atom bonding at least one aryl and wherein nitrogen atom bonding is to " ammonia diaryl base " of at least two aryl, and wherein said aryl is independently selected.
According to execution mode, in formula 1, X can be fluorine (F) atom.
Described first compound can comprise following at least one: difluoro (oxalic acid) lithium borate represented by following formula 1a, tetrafluoro (oxalic acid) lithium phosphate represented by following formula 1b and two (oxalic acid) lithium phosphate of the difluoro represented by following formula 1c:
Formula 1a
Formula 1b
Formula 1c
Compared with two (oxalic acid) lithium borate or three (oxalic acid) lithium phosphate, described first compound can comprise halogenic ingredient such as fluorine atom, and therefore, by the LiF using (utilization) to produce during charging and discharging, described first compound can form firm film on positive pole and/or negative pole.In this, described first compound can (such as, more effectively) time limit (life-span) characteristic that recycles to lithium battery be contributed significantly.
Second compound of formula 2 can comprise phosphine oxide or phosphine groups, the R in its Chinese style 2
1-R
9be substituted or unsubstituted C independently of one another
1-C
10alkyl.
Such as, described second compound can comprise at least one of three (trimethyl silyl) phosphine oxides represented by following formula 2a and three (trimethyl silyl) phosphine represented by following formula 2b:
Formula 2a
Formula 2b
In some embodiments, difluoro (oxalic acid) lithium borate of formula 1a can use (utilization) together with described second compound respectively as described first compound with three (trimethyl silyl) phosphine oxide of formula 2a.
Based on described electrolytical total weight, the amount of described first compound can be not less than 0.1 % by weight and be not more than 4 % by weight.Such as, based on described electrolytical total weight, the amount of described first compound can be about 0.1 % by weight-Yue 3.5 % by weight, in some embodiments about 1 % by weight-Yue 3 % by weight.When the amount of described first compound is within the scope of these, described first compound can form the diaphragm with suitable film resistance (resistance) on the surface of the positive pole of lithium battery, helps improve the cycle characteristics of lithium battery thus.
Based on described electrolytical total weight, the amount of described second compound can be not less than 0.1 % by weight and be not more than 4 % by weight.Such as, based on described electrolytical total weight, the amount of described second compound can be about 0.1 % by weight-Yue 3.5 % by weight, in some embodiments about 1 % by weight-Yue 3 % by weight.When the amount of described second compound is within the scope of these, described second compound can keep described electrolytical suitable viscosity and minimizing or prevent from, in positive pole and/or negative pole, side reaction occurs.
In addition, based on described electrolytical total weight, the total amount of described first compound and described second compound can be less than about 6 % by weight.When by two kinds of compound together and its total amount outside this scope time, by the excessive use (utilization) of described compound, can solubility problem be caused.In this, other side reaction can occur, and therefore, the cycle characteristics of lithium battery can deterioration.
At the migration medium that can be used as the ion related in the electrochemical reaction of described battery for the non-aqueous organic solvent in the electrolyte of lithium battery according to above-mentioned execution mode.Described non-aqueous organic solvent can be carbonate products, the compound based on ester, the compound based on ether, the compound based on ketone, the compound based on alcohol, aprotic solvent or its combination.
Described carbonate products can be linear carbonate compound, cyclic carbonate compound, fluoro carbonic ester compound or its combination.
The example of described linear carbonate compound is diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonic acid ester (EPC), methyl ethyl carbonate (MEC) and combination thereof.The example of described cyclic carbonate compound is ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinyl ethylene carbonate (VEC) and combination thereof.
The example of described fluoro carbonic ester compound is fluoroethylene carbonate (FEC), carbonic acid 1,2-bis-fluoroethylene, carbonic acid 1,1-bis-fluoroethylene, carbonic acid 1,1,2-tri-fluoroethylene, carbonic acid 1,1,2,2-tetra-fluoroethylene, carbonic acid 1-fluoro-2-methyl ethyl, carbonic acid 1-fluoro-1-methyl ethyl, the fluoro-1-methyl ethyl of carbonic acid 1,2-bis-, carbonic acid 1,1,2-tri-fluoro-2-methyl ethyl, carbonic acid trifluoromethyl ethyl and combination thereof.
Described carbonate products can comprise the combination (that is, mixture) of described linear carbonate compound and described cyclic carbonate compound.Such as, when the cumulative volume based on described non-aqueous organic solvent, when described cyclic carbonate compound is at least 20 volume %, such as 30 volume % or 40 volume %, the cycle characteristics of lithium battery can significantly improve.That is, based on the cumulative volume of described non-aqueous organic solvent, the amount of about 20 volume %-about 70 volume % described cyclic carbonate compound can be comprised.
Described carbonate products can be the mixture of described linear carbonate compound and/or described cyclic carbonate compound and described fluoro carbonic ester compound.Described fluoro carbonic ester compound can increase the dissolubility of lithium salts to improve described electrolytical ionic conductivity, and can promote the formation of film on negative pole.In some embodiments, described fluoro carbonic ester compound can be fluoroethylene carbonate (FEC).
Based on the cumulative volume of described non-aqueous organic solvent, the amount of described fluoro carbonic ester compound can be about 1 volume %-about 30 volume %.In one embodiment, when the amount of described fluoro carbonic ester compound is within the scope of this, described electrolyte has suitable viscosity with the effect providing it to expect.In some embodiments, except fluoroethylene carbonate (FEC), described non-aqueous organic solvent can comprise vinyl ethylene carbonate (VEC) further.Here, based on the cumulative volume of described non-aqueous organic solvent, the amount of described vinyl ethylene carbonate (VEC) can be about 0.1 volume %-about 10 volume %.
The example of the described compound based on ester is methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, decalactone, valerolactone, mevalonolactone, caprolactone and methyl formate.
The example of the described compound based on ether is butyl oxide, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, ethyoxyl Ethyl Methyl Ether, 2-methyltetrahydrofuran and oxolane.
The example of the described compound based on ketone is cyclohexanone.
The example of the described compound based on alcohol is ethanol and isopropyl alcohol.
The example of described aprotic solvent is methyl-sulfoxide, 1,2-dioxolanes, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, METHYLPYRROLIDONE, formamide, dimethyl formamide, acetonitrile, nitromethane, trimethyl phosphate, triethyl phosphate, trioctyl phosphate and trimester phosphate.
Described non-aqueous organic solvent can combinationally using (utilization) individually or with the non-aqueous organic solvent of at least two types.In the latter, can be depending on desired battery performance suitably regulate described in the mixing ratio of non-aqueous organic solvent of at least two types.
The described electrolyte for lithium battery can comprise lithium salts further.
The lithium ion source that described lithium salts can be used as in battery is run to make normal (such as, customary) that realize lithium battery.Described lithium salts can be any suitable lithium salts lithium battery being used usually to (utilization).Example for the lithium salts of nonaqueous electrolyte is LiCl, LiBr, LiI, LiClO
4, LiB
10cl
10, LiPF
6, CF
3sO
3li, CH
3sO
3li, C
4f
3sO
3li
,(CF
3sO
2)
2nLi, LiN (C
xf
2x+1sO
2) (C
yf
2+ysO
2) (wherein x and y is natural number), CF
3cO
2li, LiAsF
6, LiSbF
6, LiAlCl
4, LiAlF
4, chloroboric acid lithium, lower alphatic carboxylic acid lithium, tetraphenylboronic acid lithium, imide li and combination.
Described lithium salts can be about concentration use (utilization) of 2.0M to improve the performance (such as, Practical Performance) of lithium battery with about 0.1M-in described electrolyte.In one embodiment, when the concentration of described lithium salts is within the scope of this, described electrolyte has suitable conductivity and suitable viscosity for the performance improved, and can improve the mobility of lithium ion.
In some embodiments, the described electrolyte for lithium battery can comprise extra additive further to promote that stable solid electrolyte interface (SEI) or film formation are at the electrode surface to provide the cycle characteristics of improvement.
The example of described extra additive is vinylene carbonate (VC), propane sultone (PS), succinonitrile (SN), LiBF
4, there is silane compound and the silicon nitrogen silane compound (such as hexamethyldisiloxane) of functional group's (such as, acryloyl group, amino, epoxy radicals, methoxyl group, ethyoxyl or vinyl) that can form siloxane bond.These extra additives can individually or with its at least two kinds combinationally uses (utilization).
Based on the total weight of described non-aqueous organic solvent, the amount of described extra additive can be about 0.01 % by weight-Yue 10 % by weight.Such as, based on the total weight of described non-aqueous organic solvent, the amount of described extra additive can be 0.05 % by weight-Yue 10 % by weight, in some embodiments about 0.1 % by weight-Yue 5 % by weight and at some other execution modes about 0.5 % by weight-Yue 4 % by weight.But the amount of described extra additive is not particularly limited, unless described additive hinders the improvement of the capability retention comprising described electrolytical lithium battery significantly.
Described electrolyte can be applicable to the lithium battery that can run under the high voltage of at least 4.3V, to improve element cell performance and stability.Such as, described electrolyte can be applicable to the high-voltage battery that can run under about 4.3V-is about the voltage of 4.6V.
According to another execution mode, the electrolyte that lithium battery can comprise positive pole, negative pole and arrange between a positive electrode and a negative electrode.Described lithium battery can use (utilization) suitable method manufacture as known in the art.
Fig. 1 illustrates the schematic cross section according to the representative configurations of the lithium battery 30 of Example embodiments.
With reference to Fig. 1, the dividing plate 24 that lithium battery 30 comprises positive pole 23, negative pole 22 and is arranged between positive pole 23 and negative pole 22.Positive pole 23, negative pole 22 and dividing plate 24 can be reeled or fold to be contained in battery case 25.Then, battery case 25 filled with electrolyte and is sealed by seal member 26, completing the manufacture of lithium battery 30 thus.Battery case 25 can be column type, square type or film-type.Such as, lithium battery 30 can be lithium ion battery.
Positive pole 23 comprises plus plate current-collecting body and is arranged on the positive electrode active material layer on described plus plate current-collecting body.
Described plus plate current-collecting body can have the thickness of about 3 μm of-Yue 500 μm.Described plus plate current-collecting body is not particularly limited, and can be any suitable material, as long as it has suitable conductivity and does not cause chemical change in manufactured battery.The example of described plus plate current-collecting body comprises copper, stainless steel, aluminium, nickel, titanium, sintered carbon, with copper or the stainless steel of carbon, nickel, titanium and/or silver surface process, and aluminium-cadmium alloy.In addition, described plus plate current-collecting body can be processed to have tiny irregularity in its surface to strengthen the adhesion strength of described plus plate current-collecting body to described positive electrode active material layer, and can comprise film, sheet, paper tinsel, net, cell structure, foams and non-woven fleece multiple suitable form any one use (utilization).
Described positive electrode active material layer can comprise positive active material, adhesive and optional conductive agent.
Can to use in (utilization) this area and usually to use any suitable of (utilizations) to contain lithium metal oxide as described positive active material.Common positive active material can be lithium and at least one of the composite oxides of metal being selected from cobalt (Co), manganese (Mn), nickel (Ni) and combine.Such as, common positive active material can be at least one of the compound be expressed from the next: Li
aa
1-bl
bd
2(wherein 0.90≤a≤1 and 0≤b≤0.5); Li
ae
1-bl
bo
2-cd
c(wherein 0.90≤a≤1,0≤b≤0.5, and 0≤c≤0.05); LiE
2-bl
bo
4-cd
c(wherein 0≤b≤0.5 and 0≤c≤0.05); Li
ani
1-b-cco
bl
cd
α(wherein 0.90≤a≤1,0≤b≤0.5,0≤c≤0.05, and 0< α≤2); Li
ani
1-b-cco
bl
co
2-αm
α(wherein 0.90≤a≤1,0≤b≤0.5,0≤c≤0.05, and 0< α <2); Li
ani
1-b-cco
bl
co
2-αm
2(wherein 0.90≤a≤1,0≤b≤0.5,0≤c≤0.05, and 0< α <2); Li
ani
1-b-cmn
bl
cd
α(wherein 0.90≤a≤1,0≤b≤0.5,0≤c≤0.05, and 0< α≤2); Li
ani
1-b-cmn
bl
co
2-αm
α(wherein 0.90≤a≤1,0≤b≤0.5,0≤c≤0.05, and 0< α <2); Li
ani
1-b-cmn
bl
co
2-αm
2(wherein 0.90≤a≤1,0≤b≤0.5,0≤c≤0.05, and 0< α <2); Li
ani
be
cg
do
2(wherein 0.90≤a≤1,0≤b≤0.9,0≤c≤0.5, and 0.001≤d≤0.1); Li
ani
bco
cmn
dg
eo
2(wherein 0.90≤a≤1,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5, and 0.001≤e≤0.1); Li
aniG
bo
2(wherein 0.90≤a≤1 and 0.001≤b≤0.1); Li
acoG
bo
2(wherein 0.90≤a≤1 and 0.001≤b≤0.1); Li
amnG
bo
2(wherein 0.90≤a≤1 and 0.001≤b≤0.1); Li
amn
2g
bo
4(wherein 0.90≤a≤1 and 0.001≤b≤0.1); QO
2; QS
2; LiQS
2; V
2o
5; LiV
2o
5; LiTO
2; LiNiVO
4; Li
(3-f)j
2(PO
4)
3(0≤f≤2); Li
(3-f)fe
2(PO
4)
3(0≤f≤2); And LiFePO
4.
In above formula, A can be selected from Ni, Co, Mn and combination thereof; L can be selected from aluminium (Al), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), rare earth element and combination thereof; D can be selected from oxygen (O), fluorine (F), sulphur (S), phosphorus (P) and combination thereof; E can be selected from cobalt (Co), manganese (Mn) and combination thereof; M can be selected from fluorine (F), sulphur (S), phosphorus (P) and combination thereof; G can be selected from aluminium (Al), chromium (Cr), manganese (Mn), iron (Fe), magnesium (Mg), lanthanum (La), cerium (Ce), strontium (Sr), vanadium (V) and combination thereof; Q can be selected from titanium (Ti), molybdenum (Mo), manganese (Mn) and combination thereof; T can be selected from chromium (Cr), vanadium (V), iron (Fe), scandium (Sc), yttrium (Y) and combination thereof; Vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu) and combination thereof can be selected from J.
Such as, described positive active material can be LiCoO
2, LiMn
xo
2x(wherein x=1 or 2), LiNi
1-xmn
xo
2(wherein 0<x<1), LiNi
1-x-yco
xmn
yo
2(wherein 0≤x≤0.5 and 0≤y≤0.5), or LiFePO
4.
In some embodiments, described positive active material can have coating layer in its surface.Alternatively, the compound that more than (utilization) can be used to enumerate with there is the mixture of compound of coating layer as described positive active material.Described coating layer can comprise the compound being selected from following coated element: oxide, hydroxide, oxyhydroxide, carbonic acid oxonium salt and hydroxyl carbonate.Compound for described coating layer can be unbodied or crystallization.Coated element for described coating layer can be magnesium (Mg), aluminium (Al), cobalt (Co), potassium (K), sodium (Na), calcium (Ca), silicon (Si), titanium (Ti), vanadium (V), tin (Sn), germanium (Ge), gallium (Ga), boron (B), arsenic (As), zirconium (Zr) or its mixture.The physical property that described coating layer can use (utilization) adversely not affected positive active material time (utilization) when the compound of described coated element uses and be any suitable method (such as, spraying method or dipping method) known to persons of ordinary skill in the art formed.Thus, it will not be provided here to describe in detail.
Described adhesive can by positive active material particle adherence (such as, securely bond) together with bonding (such as, bonding securely) to collector.The example of described adhesive is polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylation polyvinyl chloride, polyvinyl fluoride, the polymer comprising ethylidene oxygen, PVP, polyurethane, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, butadiene-styrene rubber (SBR), acrylic modified (acroleic acid esterification) SBR, epoxy resin and nylon, but is not limited thereto.
(utilization) described conductive agent can be used to provide conductivity to electrode.(utilization) can be used not cause any suitable electrically conductive material of chemical change in the battery.The example of described conductive agent is the material based on metal (such as copper (Cu), nickel (Ni), aluminium (Al), silver (Ag) etc.) of native graphite, Delanium, carbon black, acetylene black, Ketjen black, carbon fiber and powder or fibers form.Described conductive agent can comprise the combination of single electric conducting material (such as polypheny lene derivatives) or at least two kinds of electric conducting materials.
Negative pole 22 can comprise negative current collector and be arranged on the negative electrode active material layer on described negative current collector.
Described negative current collector can have the thickness of such as about 3 μm of-Yue 500 μm.Described negative current collector is not particularly limited, and can be any suitable material, as long as it has suitable conductivity and does not cause chemical change in manufactured battery.The example of described negative current collector is copper, stainless steel, aluminium, nickel, titanium, sintered carbon, with copper or the stainless steel of carbon, nickel, titanium and/or silver surface process, and aluminium-cadmium alloy.In addition, described negative current collector can be processed to have tiny irregularity in its surface to strengthen the adhesion strength of described negative current collector to described negative electrode active material layer, and can comprise any one use (utilization) of the multiple suitable form of film, sheet, paper tinsel, net, cell structure, foams and non-woven fleece.
Described negative electrode active material layer can comprise negative electrode active material, adhesive and optional conductive agent.
Described negative electrode active material is not particularly limited, and can be selected from any suitable negative electrode active material using (utilization) in this area.The example of described negative electrode active material is lithium metal, lithium metal alloy, transition metal oxide, allow the material that the doping or go of lithium is adulterated and allow the reversible embedding of lithium ion and the material of deintercalation, and it can individually or with its at least two kinds combinationally uses (utilization).
Described lithium metal alloy can be lithium and the alloy being selected from following metal: sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), silicon (Si), antimony (antimony, Sb), plumbous (Pb), indium (In), zinc (Zn), barium (Ba), radium (Ra), germanium (Ge), aluminium (Al) and tin (Sn).
The limiting examples of described transition metal oxide is tungsten oxide, molybdenum oxide, titanium oxide, Li-Ti oxide, barium oxide and lithium-barium oxide.
Described doping of allowing lithium or the example removing the material adulterated are Si, Sn, Al, Ge, Pb, Bi, Sb, SiO
x(0<x<2), Si-Y alloy (wherein Y is alkali metal, alkaline-earth metal, the 11st race's element, the 12nd race's element, the 13rd race's element, the 14th race's element, the 15th race's element, the 16th race's element, transition metal, rare earth element or its combination, except Si), SnO
x(0<x<2) and Sn-Y alloy (wherein Y be alkali metal, alkaline-earth metal, the 11st race's element, the 12nd race's element, the 13rd race's element, the 14th race's element, the 15th race's element, the 16th race's element, transition metal, rare earth element or its combination, except Sn).Such as, Y can be magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf),
(Rf), vanadium (V), niobium (Nb), tantalum (Ta),
(Db), chromium (Cr), molybdenum (Mo), tungsten (W),
(Sg), technetium (Tc), rhenium (Re),
(Bh), iron (Fe), plumbous (Pb), ruthenium (Ru), osmium (Os),
(Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), boron (B), aluminium (Al), gallium (Ga), tin (Sn), indium (In), thallium (Tl), germanium (Ge), phosphorus (P), arsenic (As), antimony (antimony, Sb), bismuth (Bi), sulphur (S), selenium (Se), tellurium (Te), polonium (Po) or its combination.
Describedly allow that the reversible embedding of lithium ion and the material of deintercalation to can be in lithium battery any suitable carbonaceous negative electrode active material usually using (utilization).The example of such carbonaceous material be crystalline carbon, amorphous carbon, and composition thereof.The limiting examples of described crystalline carbon is native graphite, Delanium, expanded graphite, Graphene, fullerene cigarette ash, carbon nano-tube and carbon fiber.The limiting examples of described amorphous carbon is soft carbon (carbon sintered at low temperatures), hard carbon, mesophase pitch carbonized product and sintering coke.Described carbonaceous negative electrode active material can be such as spherical, flat, threadiness, tubulose or powder type.
Anode active material particles can bond by described adhesive (such as, securely bond) together with bonding (such as, bonding securely) to described negative current collector.The limiting examples of described adhesive is polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylation polyvinyl chloride, polyvinyl fluoride, the polymer comprising ethylidene oxygen, PVP, polyurethane, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, butadiene-styrene rubber (SBR), the SBR of acroleic acid esterification, epoxy resin and nylon, but is not limited thereto.
Use (utilization) described conductive agent to provide conductivity to described negative pole.(utilization) can be used not cause any suitable electrically conductive material of chemical change in the battery.The example of described conductive agent is carbonaceous material (such as native graphite, Delanium, carbon black, acetylene black, Ketjen black, carbon fiber etc.); The material based on metal (such as copper (Cu), nickel (Ni), aluminium (Al), silver (Ag) etc.) of powder or fibers form; And comprise the electric conducting material of conducting polymer (such as polypheny lene derivatives); And composition thereof.
Positive pole 23 and negative pole 22 can each via following manufactures: active material, conductive agent and adhesive are mixed in a solvent to prepare active compound composition, and by described active compound composition coating on a current collector.
The method of the electrode that (utilization) any suitable manufacture known to persons of ordinary skill in the art can be used such.Thus, it will not be provided in this article to describe in detail.Here, the example of described solvent is 1-METHYLPYRROLIDONE (NMP), acetone, He Shui, but described solvent is not limited thereto.
Dividing plate 24 can be arranged between positive pole 23 and negative pole 22, and dividing plate 24 can be any suitable dividing plate lithium battery being used usually to (utilization).Such as, dividing plate 24 can have the resistance of the low migration to the ion in electrolyte and have electrolyte retention.Dividing plate 24 can be single or multiple lift.The example of dividing plate 24 is glass fibre, polyester, teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and combination thereof, and it can be non-woven fleece or yarn fabric separately.Dividing plate 24 can have the aperture of about 0.01 μm of-Yue 10 μm and the thickness of about 3 μm of-Yue 100 μm.
As described in above execution mode, based on the total weight of described non-aqueous organic solvent, the described electrolyte for lithium battery the amount of about 0.1 % by weight-Yue 1 % by weight can comprise lithium nitrate (LiNO
3).Described electrolyte can inject to be had between the positive pole 23 of dividing plate 24 and negative pole 22 therebetween.
Except the application in mobile phone or portable computer, the suitable use (utilization) of described lithium battery can be included in the application in electric motor car, and in described electric motor car, lithium battery should run under high voltage, high-output power and high temperature.Described lithium battery also can configure together with existing internal combustion engine, fuel cell and/or ultracapacitor, for the use (utilization) in hybrid electric vehicle.Thus, by the operation under high-output power, high voltage and high temperature, described lithium battery can be applicable to electric bicycle, electric tool etc.
Now with reference to following examples, one or more execution mode is described in more detail.But these embodiments are not intended to limit the scope of described one or more execution mode.
(according to the evaluation of additive to the element cell characteristic of electrolytical mixing ratio)
embodiment 1a
Mixed solvent to the ethylene carbonate (EC) mixed with the volume ratio of about 20:20:60, propylene carbonate (PC) and diethyl carbonate (DEC) adds LiPF
6, until LiPF
6concentration reach 1.3M.Then, as additive, three (trimethyl silyl) phosphine oxide (TMSPa) of difluoro (oxalic acid) lithium borate (LiFOB) of the following formula 1a of 1.5 % by weight and the following formula 2a of 3 % by weight is added to described mixed solvent, thus for the preparation of the electrolyte of lithium battery.
Formula 1a
Formula 2a
(utilization) described electrolyte is used to prepare evaluation unit battery in the following manner.
Using the LiCoO as positive active material
2powder and carbonaceous conductive agent (Super-P; TimcalLtd.) mix with the weight ratio of 90:5, then add Kynoar (PVDF) binder solution to prepare wherein active material: carbonaceous conductive agent: the weight ratio of adhesive is the slurry of 90:5:5.Active material slurry is coated on the aluminium foil with 15 μm of thickness.Aluminium foil is dry, and roll-in is to prepare positive pole.Here, positive plate has the density (such as, mixture density) of 5.1g/cc.
In order to reduce the viscosity of the mixture of the powdered graphite as negative electrode active material and the PVDF adhesive mixed using the weight ratio of 1:1, adding 1-METHYLPYRROLIDONE solvent until its amount reaches 60 % by weight to it, preparing negative electrode active material slurry thus.Described slurry is coated on the aluminium foil with 10 μm of thickness.Aluminium foil is dry, and then roll-in is to prepare negative pole.
Then, except described electrolyte, the polyethylene separator (STAR20, Asahi) using described positive pole, described negative pole and have 20 μm of thickness manufactures the full element cell of 18650 types (kind).
embodiment 1b
Full element cell is manufactured, except using the TMSPa of the LiFOB and 1.5 % by weight of (utilization) 3 % by weight as except additive in the mode identical with embodiment 1a.
embodiment 1c
Full element cell is manufactured, except using the TMSPa of the LiFOB and 2 % by weight of (utilization) 2 % by weight as except additive in the mode identical with embodiment 1a.
embodiment 1d
Full element cell is manufactured, except using the TMSPa of the LiFOB and 3 % by weight of (utilization) 3 % by weight as except additive in the mode identical with embodiment 1a.
comparative example 1a
Full element cell is manufactured, except only using the TMSPa of (utilization) 4 % by weight as except additive in the mode identical with embodiment 1a.
comparative example 1b
Full element cell is manufactured, except only using the LiFOB of (utilization) 4 % by weight as except additive in the mode identical with embodiment 1a.
comparative example 1c
Full element cell is manufactured, except only using the LiFOB of (utilization) 5 % by weight as except additive in the mode identical with embodiment 1a.
evaluation operation example 1a: the evaluation of useful life (life-span) characteristic
The evaluation of its useful life (life-span) characteristic is carried out separately: carry out charge/discharge with 0.1C/0.1C, carry out a charge/discharge with 0.2C/0.2C and repeatedly carry out charge/discharge 140 times with 1.0C/1.0C by the following full element cell to preparing according to embodiment 1a-1d and comparative example 1a-1c.Such charge/discharge test is at the temperature of 45 DEG C and carry out as follows: with the constant voltage mode of 4.4V (relative to Li), make element cell 0.05C multiplying power cut-off, then by element cell with the constant current discharge of 1.0C multiplying power until the voltage of element cell reaches 2.75V (relative to Li).Here, useful life (life-span) characteristic is evaluated by calculating the capability retention defined by following equation 1.
Equation 1
Capability retention [%]=[n-th cyclic discharge capacity/1st time cyclic discharge capacity] × 100
The capability retention of the full battery of embodiment 1a-1d and comparative example 1a-1c is shown in Figure 2.
With reference to Fig. 2, confirm, when the total amount of LiFOB and TMSPa here mixed is no more than 6 % by weight, full element cell has useful life (life-span) characteristic of improvement.Alternatively, confirm, the excessive total amount of LiFOB and TMSPa here mixed adversely affects useful life (life-span) characteristic of full element cell.Even if be used alone (utilization) TMSPa or LiFOB, also find that its excessive amount adversely affects useful life (life-span) characteristic of full element cell.
(when by comparison in difference when TMSPa and LiFOB and LiBOB mixing)
embodiment 2
Mixed solvent to (EC) that mix with the volume ratio of about 20:20:60, propylene carbonate (PC) and diethyl carbonate (DEC) adds LiPF
6, until LiPF
6concentration reach 1.3M.Then, as additive, add the TMSPa of the LiFOB of 1.5 % by weight and 3 % by weight to described mixed solvent, thus for the preparation of the electrolyte of lithium battery.
Full element cell is manufactured in the mode identical with embodiment 1a by using (utilization) described electrolyte.
comparative example 2a
Full element cell is manufactured, except the TMSPa of pair (oxalic acid) lithium borate (LiBOB) and 3 % by weight of using the following formula 3 of (utilizations) 1.5 % by weight is as except additive in mode in the same manner as in Example 2.
Formula 3
comparative example 2b
Full element cell is manufactured, except not using (utilization) additive in mode in the same manner as in Example 2.
evaluation operation example 2: the evaluation of useful life (life-span) characteristic
By the following evaluation to carrying out its useful life (life-span) characteristic separately according to the full element cell of embodiment 2 and comparative example 2a-2b: carry out a charge/discharge with 0.1C/0.1C, carry out a charge/discharge with 0.2C/0.2C, and repeatedly carry out charge/discharge 70 times with 1.0C/1.0C.Such charge/discharge test is at the temperature of 45 DEG C and carry out as follows: with the constant voltage mode of 4.45V (relative to Li), make element cell 0.05C multiplying power cut-off, then by element cell with the constant current discharge of 1.0C multiplying power until the voltage of element cell reaches 2.75V (relative to Li).
The capability retention of the full element cell of embodiment 2 and comparative example 2a-2b is shown in Figure 3.
With reference to Fig. 3, confirm, LiFOB provides useful life (life-span) characteristic better than LiBOB.LiFOB has fluorine not to be covered (F) composition in LiBOB, and in this, LiFOB can form the good useful life (life-span) of firm film for battery on positive pole and negative pole.
evaluation operation example 3: the analysis of anode thin film composition
After first time charge/discharge, take apart to collect positive pole by each comfortable glove box of full element cell of embodiment 2 and comparative example 2a-2b, then that positive pole is clean with from its removing electrolyte and lithium salts with dimethyl carbonate, and dry.Get surfacing as sample from each positive pole, then use (utilization) x-ray photoelectron spectroscopy (XPS) (SigmaProbe, Thermo, UK) to analyze described sample under vacuum.Result is shown in Fig. 4 A and 4B.
Fig. 4 A is the XPS result at display O1s peak, and Fig. 4 B is the XPS result at display F1s peak.
With reference to Fig. 4 A and 4B, find compared with the surfacing of the surface area of the positive pole from comparative example 2b, from the surfacing of the surface area of the positive pole of the full element cell of embodiment 2 and comparative example 2a, there is larger O1s peak, and find compared with the surfacing of embodiment 2, the surfacing of the comparative example 2b prepared by using the LiBOB with more oxalate group has larger O1s peak.
Meanwhile, find that the surfacing by means of only the embodiment 2 using (utilization) LiFOB to prepare has large F1s peak.In this, find with comparative example 2a-2b those compared with, the full element cell with the embodiment 2 of the LiFOB structure comprising F composition forms LiF film on positive pole.
Therefore, about the protection of positive pole, find that LiFOB not only can form the organic film containing oxalate group, and form the inoranic membrane containing LiF, and TMSPa can suppress salt to decompose.Thus, find that the combination of LiFOB and TMSPa demonstrates the most excellent element cell performance.
(comparison in difference between the interpolation of TMSPi and multiple combination)
embodiment 3a
Mixed solvent to the ethylene carbonate (EC) mixed with the volume ratio of about 20:20:60, propylene carbonate (PC) and diethyl carbonate (DEC) adds LiPF
6, until LiPF
6concentration reach 1.3M.Then, as additive, add the TMSPa of the LiFOB of 1.5 % by weight and 3 % by weight to described mixed solvent, thus for the preparation of the electrolyte of lithium battery.
Full element cell is manufactured in the mode identical with embodiment 1a by using (utilization) described electrolyte.
embodiment 3b
Full element cell is manufactured, except using three (trimethyl silyl) phosphine (TMSPi) of the LiFOB of (utilization) the 1.5 % by weight and following formula 2b of 3 % by weight as except additive in the mode identical with embodiment 3a.
[formula 2b]
embodiment 3c
Manufacture full element cell in the mode identical with embodiment 3a, except use (utilization) 1.5 % by weight following formula 1b tetrafluoro (oxalic acid) lithium phosphate (LiTFOP) and 3 % by weight TMSPa as except additive.
Formula 1b
comparative example 3a
Full element cell is manufactured, except the TMSPa of pair (oxalic acid) lithium borate (LiBOB) and 3 % by weight of using (utilizations) 1.5 % by weight is as except additive in the mode identical with embodiment 3a.
comparative example 3b
Full element cell is manufactured, except not using (utilization) additive in the mode identical with embodiment 3a.
evaluation operation example 4: the evaluation of useful life (life-span) characteristic
By the following evaluation to carrying out its useful life (life-span) characteristic separately according to the full element cell of embodiment 3a-3c and comparative example 3a-3b: carry out a charge/discharge with 0.1C/0.1C, carry out a charge/discharge with 0.2C/0.2C, and repeatedly carry out charge/discharge 50 times with 1.0C/1.0C.Such charge/discharge test is at the temperature of 45 DEG C and carry out as follows: with the constant voltage mode of 4.45V (relative to Li), make element cell 0.05C multiplying power cut-off, then by element cell with the constant current discharge of 1.0C multiplying power until the voltage of element cell reaches 2.75V (relative to Li).
The capability retention of the full element cell of embodiment 3a-3c and comparative example 3a-3b is shown in Figure 5.
With reference to Fig. 5, confirm, the situation using (utilization) simultaneously to comprise F composition and compound and three (trimethyl silyl) phosphine oxide of oxalate group or the combination of three (trimethyl silyl) phosphine with do not use (utilization) any additive those compared with there is useful life (life-span) characteristic of improvement.In addition, although there is three (trimethyl silyl) group, find that described phosphine oxide or phosphine compound have those good (such as, significantly more excellent) useful life (life-span) characteristics than borate compound.
As mentioned above, one or more according to above Example embodiments, the electrolyte for lithium battery can be used (utilization) to help improve the cycle characteristics of the lithium battery that can run under high voltages.
Should be understood that the Example embodiments wherein described only should be considered and be not used in the object of restriction in the meaning described.Feature in each enforcement execution mode or in description should typically be considered to can be used for other similar characteristics in other Example embodiments or in.
Although described one or more Example embodiments with reference to the accompanying drawings, but those skilled in the art will appreciate that, when do not deviate from as by claims and equivalent thereof limit spirit and scope, the various changes of form and details aspect can be carried out wherein.
Claims (12)
1., for the electrolyte of lithium battery, comprising:
Non-aqueous organic solvent;
The first compound represented by formula 1; With
The second compound represented by formula 2:
Formula 1
Wherein, in formula 1,
A is boron (B) or phosphorus (P);
X is halogen atom;
When A is boron (B), n equals 1 and m equals 1;
When A is phosphorus (P), n equals 1 and m equals 2; Or n equals 2 and m equals 1;
Formula 2
Wherein, in formula 2,
R
1-R
9be selected from hydrogen, deuterium, halogen atom, hydroxyl (-OH), cyano group, nitro, amino, amidino groups, diazanyl, hydrazone group, hydroxy-acid group or its salt, sulfonic acid group or its salt, phosphate group or its salt, thiol group (-SH) ,-C (=O)-H, substituted or unsubstituted C independently of one another
1-C
60alkyl, substituted or unsubstituted C
2-C
60thiazolinyl, substituted or unsubstituted C
2-C
60alkynyl, substituted or unsubstituted C
3-C
10cycloalkyl, substituted or unsubstituted C
3-C
10heterocyclylalkyl, substituted or unsubstituted C
3-C
10cycloalkenyl group, substituted or unsubstituted C
2-C
10heterocycloalkenyl, substituted or unsubstituted C
6-C
60aryl and substituted or unsubstituted C
2-C
60heteroaryl; Be 0 or 1 with n.
2. the electrolyte of claim 1, the X in its Chinese style 1 is fluorine atom.
3. the electrolyte of claim 1, wherein said first compound comprises at least one compound represented by formula 1a to 1c:
Formula 1a
Formula 1b
Formula 1c
4. the electrolyte of claim 1, wherein in formula 2, at least one hydrogen atom of described alkyl, described thiazolinyl and/or described alkynyl is substituted independently of one another as follows: halogen atom, the C replaced by halogen atom
1-C
20alkyl, C
1-C
20alkoxyl, C
2-C
20alkoxyalkyl, hydroxyl, nitro, cyano group, amino, amidino groups, diazanyl, hydrazone group, carboxyl or its salt, sulfonyl, sulfamoyl, sulfonic acid group or its salt, phosphate group or its salt, C
1-C
20alkyl, C
2-C
20thiazolinyl, C
2-C
20alkynyl, C
1-C
20assorted alkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
6-C
20heteroaryl, C
6-C
20heteroaryloxy, C
6-C
20heteroaryloxyalkyl and/or C
6-C
20heteroarylalkyl.
5. the electrolyte of claim 1, the R in its Chinese style 2
1-R
9be substituted or unsubstituted C independently of one another
1-C
10alkyl.
6. the electrolyte of claim 1, wherein said second compound comprises at least one compound represented by formula 2a and 2b:
Formula 2a
Formula 2b
7. the electrolyte of claim 1, wherein said first formula 1a represents, and described second formula 2a represents:
Formula 1a
Formula 2a
8. the electrolyte of claim 1, wherein based on described electrolytical total weight, the amount of described first compound is not less than 0.1 % by weight and is not more than 4 % by weight, and the amount of described second compound is not less than 0.1 % by weight and is not more than 4 % by weight.
9. the electrolyte of claim 1, wherein based on described electrolytical total weight, the total amount of described first compound and described second compound is less than 6 % by weight.
10. the electrolyte of claim 1, comprises lithium salts further.
11. lithium batteries, comprising:
Positive pole;
Negative pole; With
The electrolyte of any one of claim 1-10 between described positive pole and described negative pole.
The lithium battery of 12. claims 11, wherein said lithium battery runs with the voltage range of 4.3V-4.6V.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140111045A KR102341408B1 (en) | 2014-08-25 | 2014-08-25 | Electrolyte for lithium battery, and lithium battery including the electrolyte |
| KR10-2014-0111045 | 2014-08-25 |
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| Publication Number | Publication Date |
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| CN105390746A true CN105390746A (en) | 2016-03-09 |
| CN105390746B CN105390746B (en) | 2019-10-11 |
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| CN201510526210.9A Active CN105390746B (en) | 2014-08-25 | 2015-08-25 | Electrolyte for lithium battery and the lithium battery including it |
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| Country | Link |
|---|---|
| US (1) | US9590275B2 (en) |
| EP (1) | EP2991155B1 (en) |
| KR (1) | KR102341408B1 (en) |
| CN (1) | CN105390746B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108886167A (en) * | 2016-04-12 | 2018-11-23 | 大金工业株式会社 | Electrolyte, electrochemical appliance, lithium ion secondary battery and component |
| CN111129600A (en) * | 2018-10-30 | 2020-05-08 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery |
| CN112086684A (en) * | 2020-09-16 | 2020-12-15 | 松山湖材料实验室 | Cesium-containing high-voltage lithium ion battery electrolyte composite additive, electrolyte and battery thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109860516B (en) * | 2018-12-20 | 2022-01-28 | 合肥国轩高科动力能源有限公司 | Preparation method of SEI film on surface of lithium battery electrode material and membrane electrode material |
| KR102311311B1 (en) * | 2020-04-16 | 2021-10-13 | (주)켐트로스 | Lithium Difluorobis(oxalato)phosphate 1,4-Dioxane Solvate, Process for Preparing the Same, and Electrolyte Composition Including the Same |
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| US20090286157A1 (en) * | 2008-05-16 | 2009-11-19 | Zonghai Chen | Surface modification agents for lithium batteries |
| US20090305145A1 (en) * | 2008-05-21 | 2009-12-10 | Samsung Sdi Co., Ltd. | Electrolyte for lithium ion secondary battery and lithium ion secondary battery comprising the same |
| US20100248039A1 (en) * | 2009-03-31 | 2010-09-30 | Samsung Sdi Co., Ltd. | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
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| JP4607488B2 (en) | 2003-04-25 | 2011-01-05 | 三井化学株式会社 | Nonaqueous electrolyte for lithium battery, method for producing the same, and lithium ion secondary battery |
| JP4703203B2 (en) | 2005-02-03 | 2011-06-15 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| CN102113163B (en) * | 2008-08-06 | 2015-01-21 | 三井化学株式会社 | Nonaqueous electrolyte solution and lithium secondary battery |
| KR20100093321A (en) | 2009-02-16 | 2010-08-25 | 삼성에스디아이 주식회사 | Non-aqueous electrolyte, and rechargeable lithium battery including the same |
| KR101433662B1 (en) | 2012-04-26 | 2014-08-26 | 파낙스 이텍(주) | electrolyte for lithium secondary battery and lithium secondary battery using the same |
| KR102030347B1 (en) | 2012-06-19 | 2019-11-18 | 에스케이이노베이션 주식회사 | Electrolyte for lithium secondary battery including additives,and lithium secondary battery |
-
2014
- 2014-08-25 KR KR1020140111045A patent/KR102341408B1/en active IP Right Grant
-
2015
- 2015-06-03 US US14/730,103 patent/US9590275B2/en active Active
- 2015-08-05 EP EP15179860.0A patent/EP2991155B1/en active Active
- 2015-08-25 CN CN201510526210.9A patent/CN105390746B/en active Active
Patent Citations (3)
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|---|---|---|---|---|
| US20090286157A1 (en) * | 2008-05-16 | 2009-11-19 | Zonghai Chen | Surface modification agents for lithium batteries |
| US20090305145A1 (en) * | 2008-05-21 | 2009-12-10 | Samsung Sdi Co., Ltd. | Electrolyte for lithium ion secondary battery and lithium ion secondary battery comprising the same |
| US20100248039A1 (en) * | 2009-03-31 | 2010-09-30 | Samsung Sdi Co., Ltd. | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108886167A (en) * | 2016-04-12 | 2018-11-23 | 大金工业株式会社 | Electrolyte, electrochemical appliance, lithium ion secondary battery and component |
| CN111129600A (en) * | 2018-10-30 | 2020-05-08 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery |
| CN111129600B (en) * | 2018-10-30 | 2021-02-09 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery |
| CN112086684A (en) * | 2020-09-16 | 2020-12-15 | 松山湖材料实验室 | Cesium-containing high-voltage lithium ion battery electrolyte composite additive, electrolyte and battery thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160024413A (en) | 2016-03-07 |
| CN105390746B (en) | 2019-10-11 |
| EP2991155B1 (en) | 2018-01-31 |
| EP2991155A1 (en) | 2016-03-02 |
| US20160056504A1 (en) | 2016-02-25 |
| US9590275B2 (en) | 2017-03-07 |
| KR102341408B1 (en) | 2021-12-20 |
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